Kinetic solvent isotope effects and correlations of rates of solvolyses for α-methylthio and other substituted acetyl chloridesElectronic supplementary information (ESI) available: Tables S1–S3. See http://www.rsc.org/suppdata/p2/b2/b202664n/

Ryu, Zoon Ha; Shin, Song Hee; Lee, Jong Pal; Lim, Gui Taek; Bentley, T. William

doi:10.1039/b202664n

Cited by 8 publications

(1 citation statement)

References 30 publications

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“…N -(2-Methylthioethyl)methylamine was prepared as follows. α-Methylthioacetic acid was chlorinated with thionyl chloride to give α-methylthioacetyl chloride, the product was reacted with methylamine to form N -methyl-α-(methylthio)acetamide, and the acetamide was reduced with lithium aluminum hydride to yield MTEMA . 3-Methyl-1,4-thiazane (MTZ) was prepared according to Gallego et al…”

Section: Computations and Experimentsmentioning

confidence: 99%

Conformational Characteristics and Configurational Properties of Poly(ethylene imine-alt-ethylene sulfide) and the Role of the Secondary Amine Group as a Junction of Attractive Interactions

Sasanuma

Kumagai

2007

Macromolecules

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Conformational analysis of poly(ethylene imine-alt-ethylene sulfide) (PEIES) has been carried out from ab initio molecular orbital calculations and NMR experiments for its model compound, N-(2methylthioethyl)methylamine (MTEMA). The meso-diad probability, bond conformations, and characteristic ratio of PEIES were predicted by the refined inversional-rotational isomeric state (IRIS) calculations using conformational energies determined from MTEMA. The refined IRIS scheme can treat geometrical parameters and interaction energies as a function of conformations of the present and neighboring bonds. The configurational properties of poly(ethylene imine-alt-ethylene oxide) (PEIEO), poly(N-methylethylene imine-alt-ethylene oxide), and poly(ethylene imine) (PEI) were also evaluated by the refined IRIS computations and compared with those obtained by the conventional method. So long as geometrical parameters are properly chosen, the conventional IRIS method may yield results comparable to those by the refined scheme. Spatial configurations of these polymers depend chiefly on intramolecular attractions between the heteroatoms; the characteristic ratio (〈r 2 〉 0 /nl 2 ) inversely correlates with the strength of N-H‚‚‚X (X ) O, N, or S) attraction: PEIEO with N-H‚‚‚O of -1.75 kcal mol -1 , 〈r 2 〉 0 /nl 2 ) 1.33; PEI with N-H‚‚‚N of -1.54 kcal mol -1 , 3.09; PEIES with N-H‚‚‚S of -0.97 kcal mol -1 , 5.15.

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Section: Computations and Experimentsmentioning

confidence: 99%

Conformational Characteristics and Configurational Properties of Poly(ethylene imine-alt-ethylene sulfide) and the Role of the Secondary Amine Group as a Junction of Attractive Interactions

Sasanuma

Kumagai

2007

Macromolecules

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Structure and reactivity in the hydrolyses of aliphatic carboxylic acid esters and chlorides

Regan

Watt

2007

J of Physical Organic Chem

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For hexanoic acid and its seven isomers, relative rates have been determined for acid catalysed esterification with methanol, and compared with those for saponification of the methyl esters. A good correlation between logarithms of relative rates for the two reactions is obtained, and it is suggested that the eight isomers provide a test set of compounds in which steric effects alone act on reactivity at the acyl carbon. A full set of steric parameters ($E_{\rm s}^\prime$ values) are presented. Rates of solvolyses of the acid chlorides of the isomers have been determined conductometrically in 3:1 wt:wt acetonitrile water. Logarithms of relative rates show a poor correlation with $E_{\rm s}^\prime$, and, taking into account the solvent dependence of the rates, the pattern excludes both rate‐limiting formation of a tetrahedral intermediate and rate‐limiting dissociation of chloride to form acylium ions. The remaining possibilities, a concerted process (AND N‡) and rapid reversible formation of a hydrate followed by rate‐limiting dissociation of chloride (AN + D N‡) are considered. Copyright © 2007 John Wiley & Sons, Ltd.

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Rate and product studies with 2‐adamantyl fluoroformate under solvolytic conditions

Kyong

Rhu

Kim

et al. 2007

J of Physical Organic Chem

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The specific rates of solvolysis of 2-adamantyl fluoroformate have been measured at 25.0 8C in 20 pure and binary solvents. These are well correlated using the extended Grunwald-Winstein equation, with incorporation of the N T solvent nucleophilicity scale and the Y Cl solvent ionizing power scale. The sensitivities (l ¼ 2.15 AE 0.17 and m ¼ 0.95 AE 0.07) toward the changes in solvent nucleophilicity and solvent ionizing power, and the k F /k Cl values are very similar to those previously observed for solvolyses of n-octyl fluoroformate, consistent with the addition step of an addition-elimination pathway being rate-determining. For aqueous ethanol, measurement of the product ratio allowed selectivity values (S) to be determined. The results are compared with those reported earlier for 2-adamantyl chloroformate and mechanistic conclusions are drawn.

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Kinetic solvent isotope effects and correlations of rates of solvolyses for α-methylthio and other substituted acetyl chloridesElectronic supplementary information (ESI) available: Tables S1–S3. See http://www.rsc.org/suppdata/p2/b2/b202664n/

Cited by 8 publications

References 30 publications

Conformational Characteristics and Configurational Properties of Poly(ethylene imine-alt-ethylene sulfide) and the Role of the Secondary Amine Group as a Junction of Attractive Interactions

Conformational Characteristics and Configurational Properties of Poly(ethylene imine-alt-ethylene sulfide) and the Role of the Secondary Amine Group as a Junction of Attractive Interactions

Structure and reactivity in the hydrolyses of aliphatic carboxylic acid esters and chlorides

Rate and product studies with 2‐adamantyl fluoroformate under solvolytic conditions

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